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OSU RC10
Gas phase measurements and calculations of HCl and Ferrocene
Adam Daly and Stephen KukolichChemistry DepartmentUniversity of Arizona
OSU RC10
Outline
• Motivation
• Calculations
• Results
• Conclusions
• Future Work
OSU RC10
Greenwald, II, Lokshin, B.V. J. Mol. Struc, 222 (1990) 11
OSU RC10
Introduction
Shea, J. Kukolich, S J.Chem.Phys. 78 3546
OSU RC10
Introduction
• Ferrocene C10H10Fe– Metal – Pi system between Iron and Cyclopentadienyl ligand– Has a wide use in electrochemistry and molecular catalysis of its
derivatives.– Easily sublimes at 50˚C at 1 mTorr, air and thermally stable
• Loosely bound structures– Organometallic/small molecule complexes provide rich computational
problems and models for complex long range interaction systems.
OSU RC10
Calculations
• MP2/6-311+G(d) and DFT• Partial OptimizationsUsing Gaussian 03
OSU RC10
MP2 Results
De= -955cm-1
De = -965 cm-1
De= -142 cm-1 A = 1146 MHzB = 628 MHzC = 502 MHz
A = 2123 MHzB = 404 MHzC = 404 MHz
A = 1136 MHzB = 693 MHzC = 540 MHz
OSU RC10
Experimental
• Instrumentation– Flygare-Balle PBFTMW spectrometer
• Pressure 10-7
• Sample injection ~ 1Hz
• Sample– Freshly sublimed Ferrocene– Anhydrous HCl ~1-5% in Ne at 0.8 to 1.2 atm– Temperature maintained 35-45 ˚C
OSU RC10
Experimental
OSU RC10
Predicted Spectrum using MP2/Hay-Wadt VDZ (Fe) / 6-31+G (C,H,Cl)Asymmetric top using SPCAT
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
4000 5000 6000 7000 8000 9000 10000 11000 12000
Pred
icte
d In
tens
ity
Frequency / MHz
'FERRO35.DAT'
OSU RC10
Results
• 91 transitions • 4745 – 13963 GHz
0
20
40
60
80
100
120
140
160
4000 6000 8000 10000 12000 14000
Inte
nsity
Frequency / MHz
OSU RC10
A closer look..
0
1
2
3
4
5
4000 6000 8000 10000 12000 14000
Inte
nsity
Frequency / MHz
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The first fit
0
20
40
60
80
100
120
140
160
7700 7750 7800 7850
Inte
nsity
Frequency / MHz
OSU RC10
B = 3911.410(2) MHzeqQ= -53.5(5) MHzs = 4 kHz
B = 3840.134(2) MHzeqQ= -42.1(5) MHz = 2 kHz
27.11.425.53
)()(
37
35
MHzMHz
CleqQCleqQ
Acetylene - HCl 1.281
Benzene – HCl 1.272
CClF3 1.26843
1 Legon, A.C., Aldrich, P.D. and Flygare, W.H. J. Chem. Phys. 75, 6252 Read, W. G. Campbell, E. J., Henderson, G., Flygare, W. J. J. Am. Chem. Soc. 103, 76703 Haubrich, S.T., Roehrig, M.A. Kukolich, S.G., J. Chem. Phys. 93, 121
Experimental Predicted J” K” F” J' K‘ F' Frequency Frequency Difference1 0 2 0 0 2 7671.850 7671.853 -0.003 1 0 3 0 0 2 7682.375 7682.375 -0.000 1 0 1 0 0 2 7690.796 7690.797 -0.001
Experimental Predicted J” K” F” J‘ K‘ F' Frequency Frequency Difference1 0 2 0 0 2 7812.128 7812.131 -0.003 1 0 3 0 0 2 7825.502 7825.496 0.006 1 0 1 0 0 2 7836.192 7836.195 -0.003
The first fit
OSU RC10
Lines used in the fit
0
1
2
3
4
5
4000 6000 8000 10000 12000 14000
Inte
nsity
Frequency / MHz
The second pattern
OSU RC10
The second substance
0
0.05
0.1
0.15
0.2
7000 8000 9000 10000 11000 12000 13000 14000
Pre
dict
ed In
tens
ity
Frequency / MHz
0
0.05
0.1
0.15
0.2
7000 8000 9000 10000 11000 12000 13000 14000
Pre
dict
ed In
tens
ity
Frequency / MHz
B~1745 MHz
B~872 MHz
A = 2123 MHzB = 404 MHzC = 404 MHz
OSU RC10
0
5
10
15
20
6981 6981.5 6982 6982.5 6983 6983.5 6984 6984.5 6985
Inte
nsity
Frequency / MHz
'FREQLIST.TXT'
0
1
2
3
4
5
10472 10472.5 10473 10473.5 10474 10474.5 10475
Inte
nsity
Frequency / MHz
'FREQLIST.TXT'
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
13961 13961.5 13962 13962.5 13963 13963.5 13964
Inte
nsity
Frequency / MHz
'FREQLIST.TXT'
6983 could be a J = 2->1or J= 4->3
OSU RC10
CpCl Pic herePossible Reactions
A= 4032B= 1326C = 1326
A = 7016B = 2012C = 1801MP2/6-311+G(d)
B3LYP/6-311+G(d)
OSU RC10
Summary
• The data obtained does not support that a a complex is formed from HCl and Ferrocene.
• There exists a small molecule that is produced when Ferrocene and HCl interact with B(35Cl)=3911.4 and B(37Cl)=3840.1.
• A second substance is present with symmetric top or near symmetric top with B greater than that predicted from an HCl-Ferrocene complex*
• Multiple species containing chlorine may be present.
OSU RC10
Future Work
• Testing with Ruthenocene
• Mass spectrum of the products of gas phase Ferrocene and HCl (Denton Group at U of A)
• More Scanning of a possible fit of C5H5Cl
OSU RC10
Acknowledgements
•Stephen G. Kukolich•Laszlo Sarkozy, •Chakree Tanjaroon